Siccative composition and process of making same



v Patented Dec. 8, 1936 UNITED STATES sroca'rrvn COMPOSITION AND ommxmo sum PROCESS Carleton Ellis, Montclair, N. 1., assignor to Ellis- Foster Company, a corporation of New Jersey No Drawing. Application March 23, 1932.

Serial No; 600,833

19 Claims. (o 134 -26) This invention relates to resinous coating binders of derivation as is subsequently disclosed and further relates to resinous coating binders which are soluble in aqueous alkaline solutions and 5 which when dissolved in water containing a volatile alkali such as ammonium hydroxide may be applied, with or without pigment, to surfaces as a varnish, paint, lacquer, enamel, mastic, and the like, and on evaporation of the ammonia and the water leave a firm coating.

The present invention is particularly concernedwith coatings containing chemically altered glyceride oils and/or their fatty acids or a constituent fatty acid partlcularlyunsaturated fatty -5 acids of glyce'rides, hence containing twelve or more carbon atoms in the acid molecule; specifically tung oil and/or its fatty acids altered to secure different characteristics by reaction with a compound preferably containingthe group "-CO CH= orsimilar cr analogous reactive group orbody generating'same, including the 'quinones,

such as benzoquinone and naphthoquinone, aldehydes such as acrolein and crotonaldehyde, likewise their corresponding acids, maleic and fumaric acids and anhydrides, itaconic and citraconic acids, maleinanilic acid, cin'namic acid, and

the like. Such compounds are hereinafter rer ferred to as diene reaction products, and where acids or acid anhydrides are employed in pro- I ducing such diene reaction product they are more specifically identified as acid modified deriva: tives.

The present invention is a continuation in part of the following -applications. In application,

- so] and process of making same", there is more particularly described and claimed these diene with compounds containing the group CO- 01-1: or similar or analogous reactive group or body containing same, as illustrated by the maleic acid reaction products with tung oil acids, etc., as well as compositions for-coatings containing the same.

, In applcation, Serial No. 577,403, filed Novemberf25, 1931, entitled Products of diene synthe- ,SflalNo. 549,334, filed July 7 1931, entitled FEllisis and process of making same, there is more particularly described and claimed these diene reaction products, and more particularly the natural resin diene reaction products, such as rosin maleic acid, tungoil rosin maleic acid, tun'g oil acid rosinmaleic acid andsimiIar reaction products, as well as varnish type compositions containing the same.

In application, Serial No. 581,077, filed December 14, 1931, entitled Ellisol paint and varnish and process of making same, there is more particularly described and claimed the diene'reac- .tion .products of the-type of natural resin acidmodified ingredients, such as rosin maleic acid, particularly in the form of their salts, such as ammonium salts, and particularly in solutions, as well as articles of manufacture carrying such coatings. In the instant application, there is more particularly described and claimed compositions-particularly adapted for coating purposes involving combinations of the diene-modified ingredients to produce compositions of relatively low viscosity, substantially free from soapiness; and having a high degree of-brushability enabling their utilization for coating purposes particularly.

\ Rosin maleic acid or analogous compound is a preferred ingredient of the product embraced under the present invention. This may be prepared for example, merely by heating rosin or abietic acid with'maleic acid or anhydride or analogous acid such as fumaric acid, whereupon reaction takes placeand the rosin becomes in-- creased in acidity thereby. I

'- A second. desirable ingredient is a drying oil,

preferably of an acid character such as tung maleic acid. The tung maleic acid ingredient may be prepared, for example, by heating tung Oil with maleic acid, for example, in proportions 'of to 40 parts respectively by weight, at tem peratures between. C. and the boiling point of the maleic acid, the addition of the maleic acid to the tung oil during the heating operation preferably being gradual until combination is secured. In some cases when'a siccative oil component is desired the tung maleic acid material may be replaced by polymerized oil such as may be prepared by heating tung oil and tung acids together. For example, reference is made to the preparation of resins in which a mixture of a drying oil and a drying oil fatty acid are heated togetherunder polymerizing conditions.

Thus a mixture of equal parts tung Oil and tung acids or 40 parts of the Oil and 60 parts of the acids is heated for a period 'of 10 to 20 minutesat 260 280 C. When sotreated theacid tung material which results thro polymerization no longer reacts very freely with maleic acid, in fact only a relatively small proportion as a rule of the maleic compound being capable of entering into combination.

On the other hand ordinary rosin is heated with maleic acid to a temperature of perhaps 250-270 C. to react presumablyaccording to the diene synthesis, a proportion of for example 100 parts rosin to 30 parts maleic acid by weight being used.

Tung maleic acid, especially when to per cent of maleic acid has been combined therein, is quite readily soluble in aqueous ammonium hydroxide, that is in ordinary ammonia water or dilute aqueous solutions of ammonia gas, the solution even in fairly high concentration not giving an undue viscosity. These solutions may be mixed with equal concentrated solutions of rosin maleic acid dissolved in ammonia water and the two ingredients, namely the siccative oil and the resin, will provide a water-varnish of useful properties which, if desired, may have added to it pigments which are compatible, such as lithopone, to make a paint compositiom On the other hand, if the polymerized product of tung oil tung acids is treated with ammonia, heavy viscous turbid solutions are quite likely to result which do not have the proper consistency for coating purposes, neither do they permit ready application by brushing. The addition of rosin maleic acid to such thick soapy solutions causes a very desirable change.

composition becomesmuch lower in viscosity, clarifies and the former turbid oil material or emulsion goes over into a clear liquid which can be brushed or sprayed as a coating composition.

A mixture of equal parts of the rosin maleic acid and of thepolymerized tung oil material can be used advantageously being brought into solution asa water compositionby the means of aqueous ammonia, likewise proportions may be varied over a considerable range, for example, 60 parts of the rosin maleic acid to parts of the acid oil; likewise ratios of 40:60, 70:30, 30:70,

etc., may be used;

A third type of composition involves the employment of rosin maleic acid, tung oil maleic acid and polymerized tung oil tung acids, these ponents resulting in livering.

over such primer. Or in some cases the coatings 76 There are also a considerable number of rerlns may be reversed. Likewise ordinary varnishes 'may beapplied over a priming coat of the water varnish or water paint.

of fairly high acid number made from a polyhydric alcohol such as glycerol, a polybasic acid such as phthalic anhydride, and a modifying agent such as a monobasic acid, particularly one ofthe drying oil acids. These resins (Rezyls) likewisemay be admixed with the components noted above to make a still more complex mixture of water paint or varnish.

Driers may be added as desired, including the Soligen driers made from naphthenic acids, etc.

. Example 1.'-25 parts rosin, 25 parts tung acids and 50 parts tung oil were heated to 280 C. and held at that temperature for 20 minutes. The product when cool was a clear viscous oil. On treatment with aqueous ammonia it formed a turbid emulsion-like solution which showed considerable soapiness. v5O parts of the oil were heated with 5 parts maleic acid. After this treatment a very small amount of unreacted insoluble material settled out of the oil. A 33 per cent solution in aqueous ammonia was made and was found to be clearer than that obtained from the unmaleinated material but was still somewhat turbid. The viscosity was lower. Coatings of both of these solutions were applied to surfaces and allowed to dry.

Example 2.--Equal weights of rosin, tung oil and tung acids were mixed and heated to 280 C. for 10 minutes. Portions of the product were then heated to 250 C. with 5, 10 and with 15 per cent of .maleic acid and the maleinated products were treated with aqueous ammonia.

33 per cent solutions were prepared. That obtained from the product which had been treated with 5 per cent of maleic acid was very turbid, viscous and soapy. A solution applied as a coating dried overnight to give a clear but somewhat uneven film. The rosin tung oil tung acid product which had been treated with 10 per cent maleic acid also gave a turbid, viscous and somewhat soapy solution, less so, however, than that in which 5 per cent of maleic acid was used. The treatment with 15 per cent of maleic acid did not improve the brushability of the composition and in fact the results of this example show clearly that rosin, tung oil and tung acids in some way interreact to lose to a very substantial degree their combining power for maleic acid,

In other words, these substances react by polymerization and otherwise so that conjugated double bonds are satisfied and the diene reaction with maleic acid takes place only to an incidental degree.

Erample 3.-Equal weights of tung oil and its free fatty acids were mixed and heated to 280 C. and portions of the reaction mixture were tested for solubility in ammonia immediately after reaching 280 C. and after 10 and also 20 minutes at this temperature. None of the specimens was found to be soluble in aqueous ammonia to give a clear solution. Viscous emulsions refor 20 minutes at 280 C. was treated with 5 parts of maleic acid, the temperature being raised to 250 C. The maleic acid combined only to a slight extent. A portion of the product was treated with aqueous ammonia but gave a turbid emulsion. Another portion was extracted with hot water before treatment with ammonia in order to eliminate unreacted maleic acid the ammonium salts of which would tend to salt out the oil compound. A somewhat less turbid and less viscous solution was obtained in this way.

. aocasco- From the foregoing it is evident that heat treatment of tung oil with tung acids brings about polymerization, that is, union between the free tung acids and those forming a part of the tung oil structure (whichreaction product is herein referred to as polymerized tung oil-tung acids) whereby an acid modified tung oil results and that such reaction destroys to a very large extent the ability of the tung oil or tung acid to unite with maleic anhydride in accordance with the diene synthesis.

Example 4.-Very much improved results are obtained when the acid-modifi'ed tung oil 'prepared as stated in Example 3 (without maleic acid treatment) is incorporated with rosin maleic acid. Rosin maleic acid was made by heating rosin 100 parts with maleic acid 30 parts, the temperature being carried to about 250 C. Equal parts of the rosin maleic acid and of the acidmodified tung oil referred to in the previous illustration were heated gently together for the purpose of mixing and a 40 per cent solution was made in aqueous ammonia. Instead of a turbid emulsion the composition this time was a clear fluid solution from which practically all soapiness had disappeared. The rosin maleic acid thus serves as a reducer of viscosityand acts as an eliminator of soapiness.

Example 5.--An acid-modified tung oil was made by heating equal parts by weight of tuna oil and tung acids at 260" C. for 20 minutes. A mixture was made of 30 parts of this acid-modified tung oil with. 20 parts rosin maleic acid 30 per cent maleic acid basedon the rosin) and this mixture was dissolved in aqueous ammonia to make a 40 per cent solution which was clear and relatively fluid.

Example 6.--A similar mixture of 30 parts of the rosin maleic acid and acid-modified tung oil as used in Example was heated to 220 C. with i 0.05 parts cobalt acetate. This coating composition likewise formed a clear solution in ammonia water.

' Example 7.-60 parts tung oil and Y40 parts tung acids were heated at 260 C. for 20 minutes. 30 parts of this acid-modified tung oil and 20 parts of rosin maleic acid gave a clear solution in ammonia water.

Example 8.Cobalt acetate was siniilarly.1ncorporated in the composition ofExample land the product when dissolved in dilute aqueousammonia, that is ammonia water, gave a clear solution. I

The rosin maleic acid also has a very helpful eiiect on the brushable qualities of the compositions, greatly improving the brushability of these modified tung oil products.

Example -9.50 parts each of tung acids and rosin were heated together at 280 C. for

' and soapiness and improve brushability I also may use oxidized rosin either by itself or in. admixture with rosin maleic acid for the purpose. The oxidized rosin preferably is made by 3 pulverizing rosin and exposing it to gentle heat in a current of air at a temperature below the sintering point until after several days the rosin has become readily soluble in ammonia without forming a soapy, curdy solution when prepared in. concentrated form using aqueous ammonia as the medium. Oxidized rosin of this character may be used as'follows:

Example 10.Acid-modifled tung oil was'made by heating equal parts tung oil and tung acids "until polymerization had taken place. 30 parts of this inter-polymerized product and parts oxidized rosin were mixed and made up to a solution of 40 per cent strength in aqueous ammonia. The solution was very clear in appearance and of relatively low viscosity.

Example 11 .Similarly a 40 per cent solution was made using the same proportions of oxidized rosin and the acid-modified tung oil, the latter however being made from 2 parts tung acidsto 3 parts tung oil.. The solution in ammoniawater was clear and slightly more viscous than that of Example 10.

As stated, oxidized rosin may also be used with rosin maleic acid in the foregoing compositions, for example, a mixture of equal parts of the oxidize'd rosin and the rosin maleic acid or 3:1 to 1:3, and the like, may be utilized as desired.

Example 12,-Aoid-modified tung oil made with equal parts-tung oil and tung acids 30 parts, oxidized rosin 20 parts, litharge 0.2 part and cobalt acetate 0.02 part were heated together at 200 C.

The temperature was taken to 220 C. and the batch allowed to cool. At about '120" C. 50 parts water were added thereby cooling the mixture to about 80 C. and leaving the product in asufflciently plastic condition to react readily with aqueous ammonia. Enough concentrated ammonia was added to provide a clear solution and then more water was introduced, the final solution being of 40 percent strength." This yielded a varnish which was tested in various ways, for example, by applying to sheets oi steel, the coating giving when dry a smooth film. In'another case the varnish was diluted with water to, make a 25 per cent solution and to this was added lithopone in the proportion of 5 parts to 1 part of binder. A paint of high brushability was secured which had very-good covering power.

While the invention as described above has been largely illustrated'by reference to maleic acid diene synthesizedproducts, it should be'understood that there are 'a'wIde range of com: pounds available. Thus as illustrative of diene condensation products, there may be mentioned more specifically: tung oil-maleic acid, tung oilfumaric acid, tung oil-malic acid condensation product, tung -oil-citric acid condensation product, tung oil-citraconic acid, tung oil acids-maleic acid,.blown tung oil-maleic acid, tung oil-crotonic acid, tung oil-itaconic, boiled tung oilmaleic acid; rosin maleic'acid, rosin tung oil maleic acid, rosin tung oil acids, maleic acid, abietic acid-maleic acid, and the like.

Among the features of disclosure which appear paramount in the present invention are first that tung oil and tung acids-which in natural state are very easily reacted by the diene reaction with reagents such as maleic acid or anhydride, lose that power in proportion to the degree of heat treatment to which they are subjected, it being possible in this manner to polymerize tung oil by itself or tung oil admixed with tung acids to destroy completely reactivity with maleic acid. on the other hand by regulating the degree of polymerization products may be obtained which are reactive with maleic acid in some degree. Since maleic acid is relatively costly I desire to use the minimum amount thereof consistent with appropriate solubility in ammonia water, and the like, and therefore may interpolymerize tung oil and tung acids to a predetermined degree at which point suillcient reactivity with a maleic acid remains to obtain a water-soluble coating composition without the employment of an undue proportion of maleic acid.

It should be noted that I have utilized mixtures of tung oil and tung acid in the preparation of various resinous bodies and have brought these materials to polymerizing temperatures in the course of preparation of these resinous complexes.

In addition to tung oil and tung acids which have been used herein in an illustrative way, I may, of course, employ the other drying and semi-drying oils and their free fatty acids having an appropriate degree of reactivity for the purpose, including various mixed polymers such as those which may be obtained from corn oil, soya bean oil and also from castor oil which has been partially distilled to create a condition of high unsaturation.

To the coating compositions which may be made from the foregoing either by the use of ammonia water or in some cases hydrocarbon solvents or other organic solvent vehicles, I may incorporate pigments, dyes, stains, and the like, including. lithopone, titanium oxide, aluminum bronze, and for special instances wood flour may be added which gives an oatmeal.finish. Zinc oxide and red .lead although sometimes prone to liver may be used in some cases.' The coatings may be applied to wood, plaster, cement, steel, copper, brass, aluminum and'other metals and various other surfaces and materials of construction and of use in the arts and crafts.

Coatings may be air dried or may be baked. The baked coating isespecially desirable for metal articles.

A single coat may be used in some cases and I in fact I seek to use a highly concentrated piggood finish may be obtained with one coat. Preferably, also, the composition employed for the purpose is of fairly high viscosity in order that it may be applied to the plastered surface without the necessity of first priming or sizing same. Moreover by being of a thickish consistency it may be stippled, if desired.

However, two or more coats, that is a plurality of coats, may be applied if desired with a priming coat and upper coats of a dissimilar character, including for example a priming coat of one material and an upper coat or coats of lacquer, as for example nitrocellulose lacquer or one made with theaid of cellulose acetate or cellulose propionate, cellulose ether, and the like.

Rosin maleic acid has the ability to react with ammonium carbonate when water is introduced to give a clear solution and I therefore may utilize this property in various dry compositions in which rosin maleic acid-is a prominent constituent to provide a dry powder which on addition of water will dissolve creating a paint, varnish, lacquer,

enamel or other liquid coating composition.

As pointed out'in prior application 581,077, identified above, the rosin-maleic type of combination particularly emphasized herein is illustrative of a class of diene reaction products in which natural resins may be utilized for reaction with unsaturated organic acids reactive therewith to produce the diene type reaction products. Among the natural resins, rosin is perhaps the most readily available for the diene synthesis, yielding acids of a special degree of solubility. The diene reagent which desirably comprises an unsaturated acid or acids generally is one having less'than 12 carbon atoms, normally from 3 to 10 carbon atoms when of the aliphatic series, although they may have a larger number of carbon atoms when of the aromatic or cyclic series. Usually and preferably they are crystallizable. Such initial unsaturated aliphatic acids preferably are polybasic, normally being dibasic or tribasic including maleic, fumaric, itaconic, and citraconic acids, and so forth. An extreme degree of unsaturation is represented by the more unstable acetylene-dicarboxylic acids.

What I claim is:

- 1. An ammonia-soluble composition comprising unsaturated organic acid reaction product with tung oil and unsaturated organic acid reaction product with rosin.

2. A composition as in claim 1 in which an acid .of a drying oil is the essential modifying agent for producing the acid-modified component.

-3. A composition as in claim 1 in which tung acids constitute the essential modifying agent for producing the acid-modifiedcomponent.

4. A composition containing an unsaturated organic acid reaction product with a tung compound selected from the group consisting of tung acids and tung oil capable of dissolving in or emulsifying with aqueous alkaline solutions ,to form a composition. of relatively high viscosity and a viscosity reducer therefor selected from the group consisting of oxidized rosin and a natural resin derivative of an organic acid compound containing the group COCH=CH reactive with said natural resin.

5. A composition containing the diene reaction product of a compound containing drying oil acid radicals with an organic compound containing the group COCH=CH reactive therewith, and a natural resin compolmd selected from the group consisting of oxidized rosin and a natural resin derivative of an organic compound containing the group COCH=CH- reactive with said natural resin serving in aqueous alkaline solutions of the first named derivative to reduce the viscosity of said solution.

6. A composition containing'the diene reaction product of a compound containing drying oil acid radicals with an organic compound containing.

the group CO-CH=CH- reactive therewith, and a natural resin derivative of an organic compound containing the group COCH=CH- reactive with said natural resin.

7.. A composition containing rosin reaction product with maleic acid and maleic acid reaction product with a component selected from the group consisting of tung oil, tung oil acids, and

\ polymerized tung oil-tung acids.

selected from the group consisting of tung oil.

tung oil acids,. and polymerized tung oil-tung acids.

9., A composition containing polymerized tung oil-tung acids and rosin reaction product with maleic acid.

* 10. A composition containing rosin reaction product with maleic acid, inaleio acid reaction product with a component selected from the group consisting of tung oil, tung oil acids, and polymerized tung oil-tung acids, and polymerized tung oil-tung acids.

11., An ammonia-soluble composition comprisingunsaturated organic acid reaction product with tung oil and acid-modified rosin, and a polybasic acid-polyhydric alcohol resin of high acid number.

12. A composition containing a maleic acid modified reaction product oi tung oil, tung oil acids, and rosin.

13. A composition containing the reaction product of the combination of tung oil, tung oil acids and rosin, with an organic compound containing the group --CO-CH=CH reactive therewith.

tion product with a component selected from the group consisting of tung oil, tung oil acids.

and polymerized tung oil-tung acids and oxidized rosin.

16. A composition of rosin reaction product with maleic acid and ammonium carbonate. soluhis in water to give a solution useful as a coatinz composition.

17. An ammonia-soluble composition comprising unsaturated organic acid reaction product with tung oil and oxidized rosin.

18. An ammcniacal aqueous solution contain oxidized rosin and a natural resin derivative of an organic compound containing the group --COCH==CH- reactive with said natural resin serving in aqueous alkaline solution tor the first-named derivative to reduce the viscosity of said solution.

CARLETON BELTS. 

